Sensor for diuron quantitation based on the P450 biomimetic catalyst nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine

A biomimetic sensor based on a carbon paste electrode modified with the nickel(II) 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine complex was developed as a reliable alternative technique for the sensitive and selective analysis of the herbicide diuron in environmental media. The sensor was evaluated using cyclic voltammetry and amperometric techniques. The best amperometric responses were obtained at 750 mV vs. Ag/AgCl (KClsat), using 0.1 mol L-1 phosphate buffer solution at pH 8.0. Under these conditions, the sensor showed a linear response for diuron concentrations between 9.9 × 10-6 and 1.5 × 10-4 mol L -1, a sensitivity of 22817 (±261) μA L mol-1, and detection and quantification limits of 6.14 × 10-6 and 2 × 10-5 mol L-1, respectively. The presence of the nickel complex in the carbon paste improved selectivity, stability, and sensitivity (which increased 700%), compared to unmodified paste. The applicability of the sensor was demonstrated using enriched environmental samples (river water and soil). © 2012 Elsevier B.V. All rights reserved.

Quantificação de fibrose e enfisema em pacientes com paracoccidioidomicose (PCM) pulmonar, através de imagens de tomografia computadorizada de alta resolução (TCAR)

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Field and petrographic data of 1.90 to 1.88 Ga I- and A-type granitoids from the central region of the Amazonian Craton, NE Amazonas State, Brazil

O SW do município de Presidente Figueiredo, localizado no Estado do Amazonas, Nordeste do Cráton Amazônico Central, Brasil, hospeda granitoides do tipo I de idade entre 1890 a 1898 Ma (Terra Preta Granito, Suíte Água Branca), hornblenda-sienogranitos do tipo A (Sienogranito Canoas da Suíte Mapuera), rochas vulcânicas ácidas à intermediárias (Grupo Iricoumé) e granitos rapakivi de idades entre 1883 a 1889 Ma (Granito São Gabriel da Suíte Mapuera), e rochas afins (quartzo-gabro-anortosito e diorito), além de quartzo-monzonito Castanhal, milonitos e hornfels. A fácies quartzo-diorito do granito Terra Preta foi formada por processos de mistura entre um dique quartzo-gabro sinplutônico e um granodiorito hornblenda. Glóbulos parcialmente assimilados de sienogranitos hornblenda Canoas e seus contatos com o granodiorito hornblenda Terra Preta sugerem que o sienogranito Canoas é um pouco mais jovem do que o Granito Terra Preta. Xenólitos do sienogranito Canoas no interior do Granito São Gabriel mostram que o granito é mais jovem do que o sienogranito Canoas. Novas evidências geológicas e petrográficas avançam na compreensão petrológica destas rochas e sugerem que, além de cristalização fracionada, assimilação e mistura de magma, desempenharam um papel importante, pelo menos em escala local, na evolução e variação composicionais dos plutons. Tal evidência é encontrada no Granito Terra Preta misturado com materiais quartzo-diorito, félsico associado ao sienogranito Canoas e nos enclaves microgranulares intermediários, que apresentam biotita e hornblenda primárias, além de dissolução plagioclásio, corrosão de feldspatos, mantos feldspatos alcalinos, segunda geração de apatita, e elevados teores xenocristais em enclaves intermediários formados a partir da fragmentação de intrusões máficas. Análises petrográficas mostram que um evento deformacional registrado na parte Ocidental da área de estudo (com deformação progressiva de E para W) é estimado entre o magmatismo pós-colisional de 1,90 Ga e as invasões do Granito São Gabriel e rochas afins máficas/intermediárias (intraplaca). No entanto, torna-se extremamente necessário obter idades absolutas para este evento metamórfico.

Síntese de derivados 4-aril-3,4-di-hidrocumarínicos catalisada por NbCl5

Multicomponent reactions between phenols, β-diesters and benzaldehydes for the synthesis of 4-aryl-3,4-dihydrocoumarin derivatives were carried out under mild conditions (room temperature) and presented moderate yields (38-88%) and reasonable reaction times (2-4 days), using niobium pentachloride as a catalyst.

Anticorpos naturais e infecção: anticorpos naturais na doença de Chagas e na paracoccidioidomicose

Using ELISA technique, natural antibodies against self and non self antigens were determined in 80 patients chronically intected by T. cruzi and 40 individuals suffering from a deep mycosis frequentely found in Latin Amarica (Paracoccidioidomycosis - PCM). Two forms of PCM were investigated: adult forms and juvenil type of disease. Eighty percent (80%) of the former group had significantly elevated anti-laminin antibody levels (M=4.7,SD±1.8) compared with healthy controls and different specificities of antibody were associated with anti-laminin in pathological sera. A notable binding to cytoskeletal proteins was observed, specially with band 3 and their peptides derivates, such as 62 kDa peptide. By means of Protein A chromatography we were able to show that natural anti-Gal antibodies may be bound by their Fab region to other immunoglobulins and/or to Protein A by alternative sites of binding. The finding of lgG anti-Gal antibodies in circulating immune complexes isolated from chagasic sera supported the first alternative. However, it is possible that some of lgG anti-Gal antibodies, belong to VH111 subgroup of immunoglobulins, that bind directly to Protein A. Among the 40 sera from PCM examined, the majority was considered as not exhibiting a signilicantly higher binding than normal sera to antigens tested. However thirty percent (30%) of the chronic patients had an increased levels of natural antibodies at least for one specificity such as actyn, myosin and Gala1,3Gal epitopes. ln juvenil type of PCM the mean value found for actyn was also increased 2,42 (range 1,0 to 5,3). Utilizing the polyethylene glicol precipitation the presence of circulating immune complexes was investigated in PCM sera. Specific antibodies for soluble antigens from P. brasiliensis and natural antibodies against myoglobin, myosin and Gala1,3 Gal epitopes were characterized

Evaluation of Toll-Like Receptor 2 and 4 RNA Expression and the Cytokine Profile in Postmenopausal Women with Metabolic Syndrome

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Circadian-rhythm of the endopeptidase 22.19 (ec 3.4.22.19) in the rat-brain

The endopeptidase 22.19 (EC 3.4.22.19) has been associated with the metabolism of neuropeptides by its ability to convert small enkephalin-containing peptides (8 to 13 amino acids) into enkephalins. In addition, this enzyme cleaves the Arg8-Arg9 bond of neurotensin and the Phe5-Ser6 bond of bradykinin. We analyzed the circadian variation of endopeptidase 22.19 in the whole and individual areas of the rat brain. Endopeptidase 22.19 activity was analyzed by high-performance liquid chromatography (HPLC) using bradykinin as an operative substrate. Enzymatic specific activities were analyzed by rhythmometric methods and indicate a circadian fluctuation of endopeptidase 22.19 specific activity (mU of enzyme/mg of protein) in the whole brain [p < 0.001, mesor (M) = 7.62, amplitude (A) = 2.89, and acrophase (phi) = 23:08 h], striatum (p < 0.001, M = 2.92, A = 0.62, phi-23:03 h), hypothalamus (p < 0.001, M = 3.15, A = 0.86, phi-01:12 h), periaqueductal gray matter (p < 0.005, M = 2.62, A = 0.34, phi = 22:35 h), and cerebellum (p < 0.0 14, M = 4.27, A = 0.88, phi = 17:12 h). The circadian rhythmicity in endopeptidase 22.19 specific activity suggests that light may have an effect on the peptidase activity in whole brain and in areas of the central nervous system and may be essential for the mechanisms of circadian fluctuations of neuropeptides in the brain.

Relevance of the Myeloid Differentiation Factor 88 (MyD88) on RANKL, OPG, and Nod Expressions Induced by TLR and IL-1R Signaling in Bone Marrow Stromal Cells

The myeloid differentiation factor 88 (MyD88) plays a pivotal role in Toll-like receptor (TLR)- and interleukin-1 receptor (IL-1R)-induced osteoclastogenesis. We examined the role of MyD88 on p38 mitogen-activated protein kinase (MAPK) and nuclear factor kappa-light-chain-enhancer of activated B cell (NF-κB) activation and nucleotide-binding oligomerization domain (Nod) induction by lipopolysaccharide (LPS) and IL-1 beta, and their effect on receptor activator of NF-κB ligand (RANKL) and osteoprotegerin (OPG) production in bone marrow stromal cell (BMSC). RANKL, Nod1, Nod2, NF-κB, and p38 protein levels were determined by Western blot. Nod2 was stimulated with muramyl dipeptide (MDP) prior to TLR4 stimulation with LPS. MyD88 deficiency markedly inhibited RANKL expression after LPS stimulation and increased OPG messenger RNA (mRNA) production. Also, MyD88 was necessary for NF-κB and p38 MAPK activation. MDP alone did not induce RANKL and OPG expressions; however, when combined with LPS, their expressions were significantly increased (p < 0.05). Our results support that MyD88 signaling has a pivotal role in osteoclastogenesis thought NF-κB and p38 activation. Nod2 and especially Nod1 levels were influenced by MyD88.

Relevance of the Myeloid Differentiation Factor 88 (MyD88) on RANKL, OPG, and Nod Expressions Induced by TLR and IL-1R Signaling in Bone Marrow Stromal Cells

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Investigação da funcionalidade de haplótipos no gene Interleucina 4

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Iron(III)-Pivalate-Based Complexes with Tetranuclear {Fe-4(mu(3)-O)(2)}(8+) Cores and N-Donor Ligands: Formation of Cluster and Polymeric Architectures

Different synthetic routes have been used for the preparation of a new tetranuclear [Fe4O2(O2CCMe3)(8)(bpm)] cluster (1) and a one-dimensional coordination polymer [Fe4O2-(O2CCMe3)(8)(hmta)](n) (2) (bpm = 2,2'-bipyrimidine and hmta = hexamethylenetetramine). For cluster 1, two structural isomers, 1a and 1b center dot 3MeCN, have been found. X-ray crystallographic analysis showed that all complexes consist of a central {Fe-4(mu(3)-O)(2)}(8+) core. In 1a, metal ions in the core are additionally linked by six bridging pivalates as two other pivalates and a bpm ligand are chelated to Fe-III ions, whereas in cluster 1b, metal ions in the {Fe-4(mu(3)-O)(2)}(8+) core are linked by seven bridging pivalates and only one carboxylate as well as bpm are chelated to the iron centers. In coordination polymer 2, [Fe4O2(O2CCMe3)(8)] clusters are bridged by hmta ligands to form zigzag chains. Magnetic measurements have been carried out to characterize these complexes and revealed antiferromagnetic interactions between Fe-III ions with best-fit parameters of J(wb) = -72.2 (1a) and -88.7 cm(-1) (1b) for wing...body interactions.

Local targeting of malignant gliomas by the diffusible peptidic vector 1,4,7,10-tetraazacyclododecane-1-glutaric acid-4,7,10-triacetic acid-substance p

PURPOSE: Malignant glial brain tumors consistently overexpress neurokinin type 1 receptors. In classic seed-based brachytherapy, one to several rigid (125)I seeds are inserted, mainly for the treatment of small low-grade gliomas. The complex geometry of rapidly proliferating high-grade gliomas requires a diffusible system targeting tumor-associated surface structures to saturate the tumor, including its margins. EXPERIMENTAL DESIGN: We developed a new targeting vector by conjugating the chelator 1,4,7,10-tetraazacyclododecane-1-glutaric acid-4,7,10-triacetic acid to Arg(1) of substance P, generating a radiopharmaceutical with a molecular weight of 1,806 Da and an IC(50) of 0.88 +/- 0.34 nmol/L. Cell biological studies were done with glioblastoma cell lines. neurokinin type-1 receptor (NK1R) autoradiography was done with 58 tumor biopsies. For labeling, (90)Y was mostly used. To reduce the "cross-fire effect" in critically located tumors, (177)Lut and (213)Bi were used instead. In a pilot study, we assessed feasibility, biodistribution, and early and long-term toxicity following i.t. injection of radiolabeled 1,4,7,10-tetraazacyclododecane-1-glutaric acid-4,7,10-triacetic acid substance P in 14 glioblastoma and six glioma patients of WHO grades 2 to 3. RESULTS: Autoradiography disclosed overexpression of NK1R in 55 of 58 gliomas of WHO grades 2 to 4. Internalization of the peptidic vector was found to be specific. Clinically, the radiopharmeutical was distributed according to tumor geometry. Only transient toxicity was seen as symptomatic radiogenic edema in one patient (observation period, 7-66 months). Disease stabilization and/or improved neurologic status was observed in 13 of 20 patients. Secondary resection disclosed widespread radiation necrosis with improved demarcation. CONCLUSIONS: Targeted radiotherapy using diffusible peptidic vectors represents an innovative strategy for local control of malignant gliomas, which will be further assessed as a neoadjuvant approach.

Outcome evaluation of early placed maxillary anterior single-tooth implants using objective esthetic criteria: a cross-sectional, retrospective study in 45 patients with a 2- to 4-year follow-up using pink and white esthetic scores

BACKGROUND: To validate the concept of early implant placement for use in the esthetically sensitive anterior maxilla, clinical trials should ideally include objective esthetic criteria when assessing outcome parameters. METHODS: In this cross-sectional, retrospective 2- to 4-year study involving 45 patients treated with maxillary anterior single-tooth implants according to the concept of early implant placement, a novel comprehensive index, comprising pink esthetic score and white esthetic score (PES/WES; the highest possible combined score is 20), was applied for the objective esthetic outcome assessment of anterior single-tooth implants. RESULTS: All 45 anterior maxillary single-tooth implants fulfilled strict success criteria for dental implants with regard to osseointegration, including the absence of peri-implant radiolucency, implant mobility, suppuration, and pain. The mean total PES/WES was 14.7 +/- 1.18 (range: 11 to 18). The mean total PES of 7.8 +/- 0.88 (range: 6 to 9) documents favorable overall peri-implant soft tissue conditions. The two PES variables facial mucosa curvature (1.9 +/- 0.29) and facial mucosa level (1.8 +/- 0.42) had the highest mean values, whereas the combination variable root convexity/soft tissue color and texture (1.2 +/- 0.53) proved to be the most difficult to fully satisfy. Mean scores were 1.6 +/- 0.5 for the mesial papilla and 1.3 +/- 0.5 for the distal papilla. A mean value of 6.9 +/- 1.47 (range: 4 to 10) was calculated for WES. CONCLUSIONS: This study demonstrated that anterior maxillary single-tooth replacement, according to the concept of early implant placement, is a successful and predictable treatment modality, in general, and from an esthetic point of view, in particular. The suitability of the PES/WES index for the objective outcome assessment of the esthetic dimension of anterior single-tooth implants was confirmed. However, prospective clinical trials are needed to further validate and refine this index.

Phase diagram with an enhanced spin-glass region of the mixed Ising–XY magnet LiHo{x}Er{1-x}F{4}

We present the experimental phase diagram of LiHoxEr1-xF4, a dilution series of dipolar-coupled model magnets. The phase diagram was determined using a combination of ac susceptibility and neutron scattering. Three unique phases in addition to the Ising ferromagnet LiHoF4 and the XY antiferromagnet LiErF4 have been identified. Below x = 0.86, an embedded spin-glass phase is observed, where a spin glass exists within the ferromagnetic structure. Below x = 0.57, an Ising spin glass is observed consisting of frozen needlelike clusters. For x ∼ 0.3–0.1, an antiferromagnetically coupled spin glass occurs. A reduction of TC(x) for the ferromagnet is observed which disobeys the mean-field predictions that worked for LiHoxY1-xF4.